Photomechanically active copolyimides derived from an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride

ABSTRACT

Compositions of azobenzene-containing, photomechanically active, copoly(amic acids) and linear copolyimides comprising an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride; and methods of making the same.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to the field of photomechanically active polymers. More particularly, it relates to azobenzene-containing, photomechanically active, imide copolymers derived from copolymerization of an azobenzenediamine together with a rigid dianhydride and a flexible dianhydride; and methods of making the same.

2. Description of the Related Art

Photomechanical polymers are a special class of smart polymers that are responsive to light and are capable of generating photo-directed motions and dimensional or shape alteration at the macro-scale level. The possibility of light-transduced mechanical work was first demonstrated in the literature in the mid-1960s, and since then, considerable effort has been undertaken in the synthesis of photoresponsive polymers and the characterization of their photomechanical output. The photo-directed motion and/or alteration of photomechanical polymers are driven by the collective molecular-volume change brought about by the structural rearrangement of chromophoric units upon appropriate irradiation. The chromophoric units in photoresponsive polymers are photochromic and have the unique ability to reversibly interconvert between two structural isomers (each with distinctly different optical and physical properties) under appropriate excitation conditions. Examples of chromophoric units can be found in photo-isomerizable molecules such as azobenzenes, spiropyrans, spirooxazines, diarylethylenes and fulgides. Azobenzenes are one of the most-utilized photochromic units because of their excellent thermal stability, resolved isomeric forms, and unique optical nonlinearities, as well as their ability to form surface reliefs when subjected to conventional or polarization holography. The resulting photomechanical output of a polymeric material is dependent not only on its optical properties (absorption wavelength, wavelength of exposure, polarization of exposure) but also on its molecular architecture and morphology (amorphous, crystalline, liquid crystalline) and thermomechanical properties, as well as the geometrical properties of the device, e.g. thickness of a cantilever.

Many photoresponsive polymers comprise liquid crystalline polymer networks (LCN; both glasses and elastomers), and recent reports have characterized the photomechanical and thermomechanical responses of LCN for comparatively large magnitude responses typified by bending of cantilevers or dramatic uniaxial contractions of thin films. Notably, a majority of these efforts have characterized the response of azobenzene-based LCN to exposure to UV light, which is known to decrease the order of the LCN through trans-cis photoisomerization and can result in an isothermal phase transition. UV-induced responses in azobenzene LCN are limited due to the need for multiple light sources to reverse the trans-cis isomerization.

Polyimides (PIs) represent an important class of heat-resistant polymers useful in a wide variety of applications due to their unique combination of physical properties, thermal stability, and processability, and photoresponsive polyimides and copolyimides have also been the subject of several recent reports. For example, PIs containing azobenzene in the backbone or side-chain have been investigated for photo-induced alignment in liquid crystal display (LCD), as well as nonlinear optical applications. Several cross-linked azopolyimides have also been described and reported to be photomechanically active.

SUMMARY OF THE INVENTION

The present invention includes a copoly(amic acid) having photomechanical properties with the following general formula:

in which Ar is 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and/or 3,3′,4,4′-biphenyl; R is —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and/or —O(1,4-Ph)O—; when R′ and R″ are identical, they are —H, —F, —Cl, or —CH₃, and when R′ and R″ are different, R′ is —H and R″ is —F, —Cl, —CH₃, —CF₃, and/or —OCH₃; and 0≦x≦1.0. In one embodiment of the copoly(amic acid), n is between 100 and 500.

The present invention further includes a copolyimide having photomechanical properties comprising an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride, the copolyimide having the general formula:

in which Ar is 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and/or 3,3′,4,4′-biphenyl; R is —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and/or —O(1,4-Ph)O—; when R′ and R″ are identical, they are —H, —F, —Cl, or —CH₃, and when R′ and R″ are different, R′ is —H and R″ is —F, —Cl, —CH₃, —CF₃, and/or —OCH₃; and 0≦x≦1.0. In one embodiment of the copolyimide, n is between 100 and 500. In another embodiment, 0.05≦x≦0.50.

The azobenzenediamine may be 4,4′-diaminoazobenzene, 3-fluoro-4,4′-diaminoazobenzene, 3-chloro-4,4′-diaminoazobenzene, 3-methyl-4,4′-diaminoazobenzene, 3-trifluormethyl-4,4′-diaminoazobenzene, 3-methoxy-4,4′-diaminoazobenzene, 3,3′-fluoro-4,4′-diaminoazobenzene, 3,3′-chloro-4,4′-diaminoazobenzene, and/or 3,3′-methyl-4,4′-diaminoazobenzene. The flexible dianhydride may be 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride, and/or 4,4′-(m-phenylenedioxy)diphthalic anhydride. The rigid dianhydride may be pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and/or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

In one embodiment of the copolyimide, the azobenzenediamine is 4,4′-diaminoazobenzene; the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; and the rigid dianhydride is pyromellitic dianhydride.

The present invention further includes a method for preparing copolyimides comprising the steps of: copolymerizing an azobenzenediamine with at least one rigid dianhydride and at least one flexible dianhydride to generate a copoly(amic acid) precursor solution having the general formula:

and heat-curing the copoly(amic acid) precursor solution to generate the copolyimide having the general formula:

in which Ar is 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and/or 3,3′,4,4′-biphenyl; R is —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and/or —O(1,4-Ph)O—; when R′ and R″ are identical, they are —H, —F, —Cl, or —CH₃, and when R′ and R″ are different, R′ is —H and R″ is —F, —Cl, —CH₃, —CF₃, and/or —OCH₃; and 0≦x≦1.0. In one embodiment of the method, n is between 100 and 500. In another embodiment, 0.05≦x≦0.50.

The azobenzenediamine may be 4,4′-diaminoazobenzene, 3-fluoro-4,4′-diaminoazobenzene, 3-chloro-4,4′-diaminoazobenzene, 3-methyl-4,4′-diaminoazobenzene, 3-trifluormethyl-4,4′-diaminoazobenzene, 3-methoxy-4,4′-diaminoazobenzene, 3,3′-fluoro-4,4′-diaminoazobenzene, 3,3′-chloro-4,4′-diaminoazobenzene, and/or 3,3′-methyl-4,4′-diaminoazobenzene. The flexible dianhydride may be 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, 4,4′-oxydi(phthalic anhydride), 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride, 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride, 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride, and/or 4,4′-(m-phenylenedioxy)diphthalic anhydride. The rigid dianhydride may be pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and/or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

In one embodiment of the method, the azobenzenediamine is 4,4′-diaminoazobenzene; the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; and the rigid dianhydride is pyromellitic dianhydride.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an exemplary method of synthesizing 4,4′-diaminoazobenzene.

FIG. 2 illustrates an exemplary method of synthesizing azobenzene-containing copolyimides.

FIG. 3 is a plot illustrating the stress response of Azo-PI-6FDA (●) and Azo-PI-PMDA (◯) films (5.0×0.5×0.02 mm cantilevers) upon irradiation with 100 mW/cm² of 442 nm light that is polarized 45°, parallel to, and orthogonal to the long axis of the cantilever.

FIGS. 4A and 4B demonstrate the polarization-dependent photomechanical response of an Azo-PI-6FDA film and an Azo-PI-PMDA film (5.0×0.5×0.02 mm cantilevers), respectively, upon irradiation with 100 mW/cm² of 442 nm and 488 nm light that is polarized 45°, parallel to, and orthogonal to the long axis of the cantilever.

FIGS. 5A-5E demonstrate the photo-directed bending of polyimide and copolyimide films (6.0×1.0×0.02 mm cantilevers) comprising varying ratios of PMDA:6FDA:DAAB in response to 442 nm light that is polarized parallel to the long axis of the cantilever.

FIG. 6 illustrates the relationship between the PMDA content and the bending angle demonstrated in the polyimide and copolyimide films of FIGS. 5A-5E.

DETAILED DESCRIPTION OF THE INVENTION

The present invention includes compositions of azobenzene-containing, photomechanically active, linear copolyimides and methods of making the same. The presently disclosed copolyimides demonstrate excellent photomechanical properties and distinct photomechanical responses such as polarization-controlled forward and reverse bending of a copolyimide cantilever. The present invention further demonstrates that photomechanical properties may be instilled in linear aromatic polyimides (fully imidized form) and that the extent of the photomechanical response may be controlled via the stoichiometric ratios of the rigid dianhydride (DA) and the flexible DA used in the copolymerization process.

According to the present invention, a poly(amic acid) precursor may be formed by the copolymerization of an azobenzenediamine together at room temperature with varying molar ratios of (1) a rigid dianhydride (RDA); (2) a flexible dianhydride (FDA); or (3) both a RDA and a FDA, the poly(amic acid) precursor having the following general structure A:

Following heat treatment of the poly(amic acid) precursor solution, azobenzene-containing polyimides and copolyimides having the following general structure B may be formed:

In structures A and B, x indicates the mole fraction of the RDA component; 1−x indicates the mole fraction of the FDA component; and n indicates the overall degree of polymerization (DP) of the parent polymers (x=1 for Azo-PI-RDA; x=0 for Azo-PI-FDA) or the co-polymers. The polymers having general structure B are designated throughout as Azo-PI-RDA or Azo-PI-FDA for the “parent” polyimides, and for the associated copolyimides, Azo-coPI-xx, where xx corresponds to the molar fraction (%) of RDA with respect to the FDA in the copolymer. In one embodiment, x is between 0 and 1.0. In another embodiment, 0≦x≦1.0. In a further embodiment, 0.05≦x≦0.50. In another embodiment, n may be between 100 and 500.

In both structures, Ar may be 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and/or 3,3′,4,4′-biphenyl. The linking group R may include but is not limited to the following moieties: —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and/or —O(1,4-Ph)O—. Within the same polymer, R′ and R″ may be the same moiety, or they may be different. Where R′ and R″ are the same, they are each —H, —F, —Cl, or —CH₃. Where R′ and R″ are different, R′ is —H, and R″ is —F, —Cl, —CH₃, —CF₃, and/or —OCH₃.

In structures A and B, the azobenzenediamine may be 4,4′-diaminoazobenzene (DAAB) or a derivative of DAAB, including, but not limited to 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene; 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene, and 3,3′-methyl-4,4′-diaminoazobenzene.

The flexible dianhydride (FDA) may be a bis(phthalic) anhydride having the following general structure:

The FDA may be 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′,4,4′-(p-phenylenedioxy)diphthalic anhydride; and/or 4,4′-(m-phenylenedioxy)diphthalic anhydride.

The RDA may be selected from the following aromatic dianhydrides: pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; and/or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

DAAB (III) may be synthesized as shown in FIG. 1 and described below in Example 1. In one embodiment, DAAB may be combined with a RDA such as pyromellitic dianhydride (PMDA) to form an Azo-PI-PMDA polyimide as described below in Example 2. In another embodiment, DAAB may be combined with a FDA such as 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane (6FDA) to form an Azo-PI-6FDA polyimide as described below in Example 3.

In a further embodiment, DAAB may be combined in various stoichiometric ratios with a RDA and a FDA to form an Azo-coPI-xx copolyimide. For example, as described below in Example 4 and shown in FIG. 2, PMDA (IV) and 6FDA (V) are mixed to form a copoly(amic acid) precursor solution (PAA solution, VI), and after heat treatment of the PAA solution (VI), copolyimides comprising PMDA-DAAB-6FDA (VII) in varying molar ratios may be prepared.

The present invention further includes methods of making copolyimides comprising the steps of copolymerizing an azobenzenediamine with a rigid dianhydride and a flexible dianhydride to generate a copoly(amic acid) precursor solution having the following general structure A:

and curing the copoly(amic acid) precursor solution using heat to generate a copolyimide having the following general structure B:

In structures A and B, x indicates the mole fraction of the RDA component; 1−x indicates the mole fraction of the FDA component; and n indicates the overall DP of the parent polymers (x=1 for Azo-PI-RDA; x=0 for Azo-PI-FDA) or the co-polymers. In one embodiment of the method, x is between 0 and 1.0. In another embodiment, 0≦x≦1.0. In a further embodiment, 0.05≦x≦0.50. In another embodiment, n may be between 100 and 500. In both structures, Ar may be 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and/or 3,3′,4,4′-biphenyl. The linking group R may include but is not limited to the following moieties: —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and/or —O(1,4-Ph)O—. Within the same polymer, R′ and R″ may be the same moiety, or they may be different. Where R′ and R″ are the same, they are each —H, —F, —Cl, or —CH₃. Where R′ and R″ are different, R′ is —H, and R″ is —F, —Cl, —CH₃, —CF₃, and/or —OCH₃.

In structures A and B, the azobenzenediamine used in the method of making copolyimides may be 4,4′-diaminoazobenzene (DAAB) or a derivative of DAAB, including, but not limited to 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene, 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene; and 3,3′-methyl-4,4′-diaminoazobenzene.

The flexible dianhydride (FDA) may be a bis(phthalic) anhydride having the following general structure:

The FDA may be 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′,4,4′-(p-phenylenedioxy)diphthalic anhydride; and/or 4,4′-(m-phenylenedioxy)diphthalic anhydride.

The RDA may be selected from the following aromatic dianhydrides: pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; and/or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.

The following examples and methods are presented as illustrative of the present invention or methods of carrying out the invention, and are not restrictive or limiting of the scope of the invention in any manner. Referring to the drawings, like reference numerals may designate like or corresponding parts throughout the several views.

Example 1 Synthesis of 4,4′-Diaminoazobenzene (DAAB)

4,4′-diaminoazobenzene (DAAB, III) is synthesized via a two-step route shown in FIG. 1. Glacial acetic acid (500 mL), 4′-aminoacetanilide (I) (29.0 g, 0.19 mol), sodium perborate tetrahydrate (40 g, 0.26 mol) and boric acid (10 g, 0.16 mol) are added to a 1 L three-necked round-bottomed flask equipped with a magnetic stir bar, a condenser, and a thermometer. The mixture is heated with stirring to 50-60° C. and held at this temperature for 6 hours. After the mixture is allowed to cool to room temperature, the yellow product is collected on a Büchner funnel and washed with water until the washings are neutral as indicated by pH paper. The product is then dried in a vacuum oven at 110° C. to afford 16.7 g. (58%) of 4,4′-bis(acetamido)azobenzene (II), m.p. 289.4-290.0° C. (dec.). ¹H-NMR (DMSO-d₆, δ in ppm): 2.08 (s, 6H, CH₃), 7.76-7.83 (m, 8H, Ar—H), 10.25 (s, 2H, NH).

Without further purification, 4,4′-bis(acetamido)azobenzene (II) (16.0 g, 0.054 mol) is placed in a 500-mL round-bottomed flask equipped with a condenser and a magnetic stirrer, along with methanol (150 mL) and 6N hydrochloric acid (150 mL). The mixture is heated under reflux for 1.5 hours. The reaction mixture is cooled, and the violet solid is collected on a Büchner funnel. The mixture is heated under reflux for 1.5 hours. The reaction mixture is cooled, and the violet solid collected on a Büchner funnel. The damp product is suspended in 500 mL of water in a 1 L beaker equipped with a stirrer, and the mixture is slowly neutralized by the addition of 2.5N sodium hydroxide, during which the salt dissolves and the free base separates. The crude product is collected on a Büchner funnel, washed with water, and dried under reduced pressure. The yellow powder is then recrystallized from N-methylpyrrolidinone to afford yellow crystals of DAAB (III) (8.8 g, 42%), m.p. 244.5-247.9° C. (dec.). FT-IR (KBr, cm⁻¹): 3417, 3333, 3212 (NH₂), 3040, 1627, 1592, 1502, 1294, 1150, 839. ¹H-NMR (DMSO-d₆, δ in ppm): 5.72 (s, 4H, NH₂), 6.61-6.63 (d, 4H, Ar—H), 7.51-7.53 (d, 4H, Ar—H). ¹³C-NMR (DMSO-d₆, δ in ppm): 113.4, 123.7, 143.1, 150.9. Purification of (III) by column chromatography met with limited success due to its poor solubility in most organic solvents.

Example 2 Synthesis of PMDA-DAAB Polyimide (Azo-PI-PMDA)

As shown in FIG. 2, DAAB (III) (0.8490 g, 4.000 mmol) and dimethylacetamide (DMAc) (12 mL) are added to a 50 mL 3-necked flask equipped with a magnetic stirrer and nitrogen inlet and outlet and stirred under dry nitrogen at room temperature for 30 minutes. Pyromellitic dianhydride (PMDA, IV) (0.8725 g, 4.000 mmol) is then charged. The dark red solution is agitated at room temperature for 24 hours to afford a viscous poly(amic acid) precursor solution (PAA solution, VI). The PAA solution (VI) is diluted with additional DMAc (6 mL) and poured into a glass dish, followed by vacuum evaporation of the DMAc at 50° C. and heat-treatment on the following schedule: 100° C./2 hours, 150° C./2 hours, 175° C./1 hour, 200° C./2 hours, 250° C./1 hour, and 300° C./1 hour to form imidized polymers (VII, x=1.0). The film thickness is approximately 20-100 μm. FT-IR (KBr, cm⁻¹): 3070, 1778, 1709, 1598, 1360, 1114, 1088, 821, 717, 551.

Example 3 Synthesis of 6FDA-DAAB Polyimide (Azo-PI-6FDA)

Using the same procedure as described above in Example 2 and shown in FIG. 2, a 6FDA-DAAB polyimide (VII, x=0) is prepared from DAAB (III) (0.8490 g, 4.000 mmol), 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane (6FDA, V) (1.777 g, 4.000 mmol), and DMAc (18 mL). The film thickness is approximately 20-100 μm. FT-IR (KBr, cm⁻¹): 3072, 1785, 1720, 1600, 1498, 1356, 1251, 1189, 1141, 1080, 838, 719.

Example 4 Synthesis of Azobenzene-Containing Copolyimides (PMDA:6FDA=50:50, Azo-coPI-50)

As shown in FIG. 2, DAAB (III) (0.8490 g, 4.000 mmol) and DMAc (12 mL) are added to a 50 mL, 3-necked flask equipped with a magnetic stirrer and nitrogen inlet and outlet and stirred under dry nitrogen at room temperature for 30 minutes. PMDA (IV) (0.4362 g, 2.000 mmol) and 6FDA (V) (0.8888 g, 2.000 mmol) are then charged. The dark red solution is agitated at room temperature for 24 hours to afford a viscous copoly(amic acid) precursor solution (PAA, VI). The PAA solution (VI) is diluted with DMAc (6 mL) and poured into a glass dish, followed by vacuum evaporation of DMAc at 50° C. and heat-treatment on the following schedule: 100° C./2 hours, 150° C./2 hours, 175° C./1 hour, 200° C./2 hours, 250° C./1 hour, and 300° C./1 hour to form the imidized polymers (VII, Azo-coPI-50, x=0.50). The film thickness is approximately 20-100 μm. FT-IR (KBr, cm⁻¹): 3071, 1779, 1717, 1599, 1498, 1352, 1298, 1252, 1207, 1189, 1143, 1111, 1082, 914, 891, 528.

Example 5 Physical Characterization of Polyimide and Copolyimide Films

Density Determination

The density of each polymer film is determined based on Davy's principle of hydrostatic suspension using a mixture of carbon tetrachloride and ethanol as the suspension medium. Small pieces of azopolyimide film are suspended individually in a mixture of carbon tetrachloride and methanol in a 10 mL graduated cylinder, which had previously been tared. The total solvent volume is between 9.4 and 10 mL, and the films re suspended around the 5 mL mark when the solvent is weighed. The mass of the solution and the total volume are used to calculate a density. The films did not swell in the solvent mixture. The resulting density values for the azopolyimide films are summarized in Table 1 below.

Crystallinity

The degree of crystallinity (crystallinity index) is determined by deconvoluting the wide-angle x-ray diffraction (WAXD) patterns into individual diffraction peaks (data not shown). The percent crystallinity (P_(c)) measurements are listed below in Table 1 for polyimides Azo-PI-PMDA and Azo-PI-6FDA and copolyimides Azo-coPI-xx comprising varying ratios of PMDA:6FDA. The Azo-PI-PMDA sample is a semicrystalline azopolyimide with a repeat unit of approximately 17.9 Å based on the WAXD diffraction, which is same as that calculated for the imide unit in the trans configuration. The presence of four orders of the repeat unit in the Azo-PI-PMDA sample indicates that the system is highly ordered. On the other hand, the Azo-PI-6FDA sample is totally amorphous. As 6FDA content increases, the azopolyimide films change from semi-crystalline (P_(c)=15.3, 35.5) to slightly semicrystalline (P_(c)=2.5, 2.6) to amorphous (P_(c)=0). As further shown in Example 6 and Table 1 below, the density and T_(g) decrease with an increase in the 6FDA content, which is indicative of the increasing trend in the free volume for this series of copolyimides.

Dynamic Mechanical Analysis (DMA)

DMA of the polyimide and copolyimide films is conducted in a nitrogen atmosphere with a heating rate of 4° C./min on a TA Instruments® DMA Q400EM to obtain the glass transition temperature and the storage modulus. The glass transition temperature (T_(g)) is measured from the peak value of the tan δ curve. The DMA results are summarized in Table 1 below.

Thermogravimetric Analysis (TGA)

Thermal stability of the polyimides and copolyimides is studied by TGA. The films are heated in both nitrogen and air with a heating rate of 10° C./min. The polymers show excellent short-term thermal/thermo-oxidative stability. No thermal or thermo-oxidative degradation is observed up to 450° C. in air and 420° C. in nitrogen atmosphere (results not shown).

UV Absorption Analysis

UV-vis absorption analysis is conducted for thin films of polyimides and copolyimides (data not shown). The Azo-PI-6FDA film shows a well-defined absorption transition ?_(max) at 340 nm. However, the Azo-PI-PMDA film and Azo-coPI-50 and Azo-coPI-75 copolyimide films all show broad absorption bands centered around 350 nm and visible absorption bands tailing into approximately 600 nm, which is attributable to charge-transfer complexation absorptions that result in the orange-red color of the films.

Example 6 Photomechanical Characterization of Polyimide and Copolyimide Cantilevers

For all photomechanical benchmarking experiments, azopolyimide films in the form of cantilevers are held at approximately the same distance from a source of light. The employed is blue-green irradiation, which allows all-optical control of forward and reverse bending (or contractile and expansive stress) by adjusting the orientation of the linear polarization of the irradiating light. Blue-green irradiation is also known to induce trans-cis-trans reorientation of azobenzene chromophores

The photomechanical response is first examined in tension by placing cantilevers comprising Azo-PI-6FDA and Azo-PI-PMDA (6.0×1.0×0.02 mm) in a strain-controlled dynamic mechanical analyzer (TA Instruments® RSA III). To ensure no slack during testing, the films are held with 4×10⁻⁵% strain to pretension the film. The materials are irradiated with light from an Argon-ion laser beam that is polarized 45° (E45x), parallel (E//x) to, or orthogonal (E⊥x) to the long axis of the cantilever. FIG. 3 is a plot illustrating the stress response of an Azo-PI-6FDA (●) and an Azo-PI-PMDA (◯) cantilever upon irradiation with 100 mW/cm² of 442 nm light, in which the polarization is aligned 45°, parallel to, and orthogonal to the long axis of the cantilever. Both materials generate little or no stress upon exposure to light polarized 45° to the long axis of the cantilever. However, when the polarization is rotated (under continuous irradiation) such that it is parallel to the long axis of the cantilever, the Azo-PI-6FDA film shows approximately three times the amount of contractile stress compared to its Azo-PI-PMDA film counterpart (260 kPa vs. 100 kPa, respectively). Rotation of the polarization so that is orthogonal (once again, under continuous irradiation) to the long axis of the cantilever results in expansive stress of 265 kPa for the Azo-PI-6FDA film and 105 kPa for the Azo-PI-PMDA film. In contrast to previous examinations of stress in azo-LCN materials upon exposure to blue-green irradiation, the stress of approximately 260 kPa is an order of magnitude enhancement. This higher photomechanical motion for the Azo-PI-6FDA film may be attributed to its amorphous structure as well as its lower density and T_(g) (see Table 1 below).

FIGS. 4-6 illustrate the photomechanical response of azopolyimide films without tension. As shown in FIGS. 4A and 4B, Azo-PI-6FDA and Azo-PI-PMDA exhibit similar photoresponse trends upon exposure to linearly polarized 442 nm as compared to 488 nm irradiation. Both cantilevers (5.0×0.5×0.02 mm) are initially exposed to blue-green light polarized 45° (E45x) to the long axis of the cantilever. Consistent with the stress response curves in FIG. 3, almost no bending is observed for either material upon irradiation with 442 or 448 nm light polarized 45° to the axis. Upon exposure to light polarized parallel to or orthogonal to the long axis of cantilever, the Azo-PI-6FDA film (FIG. 4A) exhibits bidirectional movement, bending 26° in approximately 60 minutes (E//x) and bending the other direction to −15° (E⊥x). Although FIG. 3 indicates that irradiation of the Azo-PI-PMDA film with light parallel to and orthogonal to the cantilever axis does generate stress, the Azo-PI-PMDA film (FIG. 4B) remains largely unresponsive at both wavelengths in terms of bending angle.

FIGS. 5A-E illustrate the photo-directed bending of polyimides and copolyimide films (5.0×1.0×0.02 mm cantilevers) comprising varying ratios of PMDA:6FDA:DAAB in response to 442 nm light that is polarized parallel to the long axis of the cantilevers, while FIG. 6 illustrates the relationship between PMDA content and the radiation of curvature (bending angle) of the polyimide and copolyimide cantilevers of FIGS. 5A-E. In general, the bending angle increases with 6FDA content. While the Azo-PI-PMDA film (5E) bends very slightly, the bending angles increase with 6FDA content to 7° for 25% 6FDA (5D), 20° for 50% 6FDA (5C), 65° for 75% 6FDA (5B), and 68° for 100% 6FDA (5A), which is reflected in the plots in FIG. 6 (see also Table 1 below). Incorporation of increasing amounts of the more flexible 6FDA units into the polymer chains results in higher free volume and, in turn, higher bending angles. This flexibility of the 6FDA molecules makes them less inclined to form interchain charge-transfer complexation, which further accounts for the higher bending angles. In addition, comparison of the results obtained from physical characterization of the azopolyimide films with the photomechanical results reveals that the bending angle is independent of the modulus. The modulus increases as crystallinity increases, which should result in an increase in photogenerated stress and thus an increase in bending angle. However, as seen in FIGS. 3-6, the opposite result occurs. Increasing crystallinity reduces the ability of the macromolecular system to translate light into work, indicating the complex relationship of crystallinity, polymer content, and polymer network morphology and their effect on the efficacy of photoisomerization and resulting photomechanical response.

The physical properties of the azobenzene-containing polyimides and copolyimides according to the present invention are summarized below in Table 1. In general, the T_(g) value and storage modulus of the presently disclosed azopolyimides greatly exceed those of previously examined glassy azo-LCN materials, as well as crosslinked, azobenzene-functionalized polyimides. In particular, the azopolyimides comprising a higher percentage of 6FDA demonstrated superior photoresponsivity and ability to translate light into work.

TABLE 1 Composition and Physical Properties of Azobenzene-Containing Polyimides and Copolyimides DAAB PMDA 6FDA ρ T_(g) E’ P_(c) Bending Angle (mol %) (mol %) (mol %) (g/cm₃) (° C.) (GPa) (%) (E//x,°) Azo-PI-6FDA 50 0 50 1.428 362 3.80 0 68 Azo-coPI-25 50 12.5 37.5 1.430 373 3.87 2.5 65 Azo-coPI-50 50 25 25 1.432 379 4.12 2.6 20 Azo-coPI-75 50 37.5 12.5 1.446 411 4.94 15.3  7 Azo-PI-PMDA 50 50 0 1.465 >450 6.12 35.5  1

Although this invention has been described with respect to certain preferred embodiments, various other embodiments and various changes and modifications to the disclosed embodiment(s) will become apparent to those skilled in the art. All such other embodiments, changes, and modifications are intended to come within the spirit and scope of the appended claims 

What is claimed is:
 1. A copolyimide having photomechanical properties and comprising an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride, the copolyimide having the general formula:

wherein Ar is at least one of 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and 3,3′,4,4′-biphenyl; wherein R is at least one of —C(CF₃)₂—, —O—, >C═O, >SO₂, —OPh-C(CF₃)₂—PhO—, —OPh-C(CH₃)₂—PhO—, >C(CF₃)Ph, —O(1,3-Ph)O—, and —O(1,4-Ph)O—; wherein R′ and R″ are —H, —F, —Cl, or —CH₃ when R′ and R″ are identical, or wherein R′ is —H and R″ is at least one of —F, —Cl, —CH₃, —CF₃, and —OCH₃ when R′ and R″ are different; and wherein 0.05≦x≦0.50.
 2. The copolyimide of claim 1 wherein n is between 100 and
 500. 3. The copolyimide of claim 1 wherein the azobenzenediamine comprises at least one of 4,4′-diaminoazobenzene; 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene; 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene; or 3,3′-methyl-4,4′-diaminoazobenzene.
 4. The copolyimide of claim 1 wherein the flexible dianhydride comprises at least one of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride; or 4,4′-(m-phenylenedioxy)diphthalic anhydride.
 5. The copolyimide of claim 1 wherein the rigid dianhydride comprises at least one of pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.
 6. The copolyimide of claim 1 wherein the azobenzenediamine is 4,4′-diaminoazobenzene, the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, and the rigid dianhydride is pyromellitic dianhydride.
 7. A method for preparing the copolyimide of claim 1, comprising: copolymerizing the azobenzenediamine with the rigid dianhydride and the flexible dianhydride to generate a copoly(amic acid) precursor having the general formula:

and heat-curing the copoly(amic acid) precursor to generate the copolyimide of claim
 1. 8. The method of claim 7 wherein n is between 100 and
 500. 9. The method of claim 7 wherein the azobenzenediamine comprises at least one of 4,4′-diaminoazobenzene; 3-fluoro-4,4′-diaminoazobenzene; 3-chloro-4,4′-diaminoazobenzene; 3-methyl-4,4′-diaminoazobenzene; 3-trifluormethyl-4,4′-diaminoazobenzene; 3-methoxy-4,4′-diaminoazobenzene; 3,3′-fluoro-4,4′-diaminoazobenzene; 3,3′-chloro-4,4′-diaminoazobenzene; or 3,3′-methyl-4,4′-diaminoazobenzene.
 10. The method of claim 7 wherein the flexible dianhydride comprises at least one of 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; 4,4′-oxydi(phthalic anhydride); 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane dianhydride; 4,4′-(2,2,2-trifluoro-1-phenylethylidene)diphthalic anhydride; 2,2′4,4′-(p-phenylenedioxy)diphthalic anhydride; or 4,4′-(m-phenylenedioxy)diphthalic anhydride.
 11. The method of claim 7 wherein the rigid dianhydride comprises at least one of pyromellitic dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; or 1,1′-biphenyl-3,3′,4,4′-tetracarboxylic acid dianhydride.
 12. The method of claim 7 wherein the azobenzenediamine is 4,4′-diaminoazobenzene, the flexible dianhydride is 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, and the rigid dianhydride is pyromellitic dianhydride.
 13. A copolyimide having photomechanical properties and comprising a 4,4′-diaminoazobenzene, 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane, and pyromellitic dianhydride, and having a general formula:

wherein R′ and R″ are —H, —F, —Cl, or —CH₃ when R′ and R″ are identical, or wherein R′ is —H and R″ is at least one of —F, —Cl, —CH₃, —CF₃, and —OCH₃ when R′ and R″ are different; and wherein 0.05≦x≦0.50.
 14. A copoly(amic acid) of claim 1, further comprising a 4,4′-diaminoazobenzene; 2,2-bis(phthalic anhydride)-1,1,1,3,3,3-hexafluoroisopropane; and pyromellitic dianhydride, the copoly(amic acid) having a general formula:

wherein R′ and R″ are —H, —F, —Cl, or —CH₃ when R′ and R″ are identical, or wherein R′ is —H and R″ is at least one of —F, —Cl, —CH₃, —CF₃, and —OCH₃ when R′ and R″ are different; wherein 0.05≦x≦0.50 and wherein 100≦n≦500. 